CN114031637A - Continuous hydrolysis method of glyphosate - Google Patents
Continuous hydrolysis method of glyphosate Download PDFInfo
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- CN114031637A CN114031637A CN202111308664.0A CN202111308664A CN114031637A CN 114031637 A CN114031637 A CN 114031637A CN 202111308664 A CN202111308664 A CN 202111308664A CN 114031637 A CN114031637 A CN 114031637A
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 25
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000007062 hydrolysis Effects 0.000 title description 8
- 238000006460 hydrolysis reaction Methods 0.000 title description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000003377 acid catalyst Substances 0.000 claims abstract description 24
- 238000009833 condensation Methods 0.000 claims abstract description 23
- 230000005494 condensation Effects 0.000 claims abstract description 23
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000004471 Glycine Substances 0.000 claims abstract description 16
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 phosphate ester Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 2
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000005080 plant death Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for continuously hydrolyzing glyphosate, which belongs to the technical field of pesticide preparation and comprises the following steps: firstly, sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 35-50 ℃, and cooling after a reaction solution is clarified; adding glycine, heating to 50-60 ℃, and cooling after the reaction liquid is clarified; adding dimethyl phosphite, heating to 45-55 ℃, cooling after the reaction liquid is clarified to obtain condensation liquid; secondly, adding an acid catalyst into the obtained condensation liquid at the temperature of 20-25 ℃, and reacting at the temperature of 40-50 ℃. The modified carrier is used as a raw material, p-toluenesulfonic acid is loaded to prepare the acid catalyst, so that the generation of chloride is avoided from the source, the alkali consumption is reduced, and the cleanness of the production process is expected to be realized. Meanwhile, the process flow is shortened, and the energy consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a continuous hydrolysis method of glyphosate.
Background
Glyphosate is a non-selective and residue-free biocidal herbicide, is very effective on perennial rooting weeds, and is widely used in rubber, mulberry, tea, orchards and sugarcane fields. Mainly inhibits enol pyruvyl shikimic acid phosphate synthetase in plants, thereby inhibiting the conversion of shikimic acid to phenylalanine, tyrosine and tryptophan, interfering protein synthesis and leading to plant death. The glyphosate is combined with metal ions such as iron, aluminum and the like to lose activity, and has no adverse effect on seeds and soil microorganisms hidden in soil.
The glyphosate is prepared by taking dimethyl phosphite, methanol, hydrochloric acid and the like as raw materials through the reaction processes of depolymerization, condensation, esterification, acidolysis and the like. However, this production process ends up having a large amount of Cl in the mother liquor wastewater-、Na+、PO4 -4Plasma of Cl-Hydrochloric acid hydrolysis process from glyphosate production; na (Na)+The neutralization step is generated by adding alkali into the filtrate; PO (PO)3 -4Mainly by the side reaction products in the production process of glyphosate. Cl-The metal oxide has the characteristics of small ionic radius and strong penetrating power, and is easy to adsorb on a passivation film to form soluble chloride to corrode metal equipment.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides a method for continuously hydrolyzing glyphosate.
The purpose of the invention can be realized by the following technical scheme:
a method for continuously hydrolyzing glyphosate comprises the following steps:
step one, condensation: sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 35-50 ℃, and cooling to 30-40 ℃ after a reaction solution is clarified; adding glycine, heating to 50-60 deg.C, and cooling to 35-40 deg.C after reaction solution is clarified; adding dimethyl phosphite, heating to 45-55 ℃, cooling to 30-45 ℃ after the reaction liquid is clarified to obtain condensation liquid;
step two, hydrolysis: adding an acid catalyst into the obtained condensation liquid at the temperature of 20-25 ℃, then heating to 40-50 ℃, reacting for 7 hours, and after the reaction is finished, filtering, crystallizing, suction filtering, washing and drying to obtain the glyphosate technical product.
Further, the dosage ratio of methanol, paraformaldehyde, triethylamine, glycine and dimethyl phosphite is 20 mL: 1.5 g: 2.5 g: 2-3 g: 3.5 g; the mass ratio of the acid catalyst to the glycine is 1: 2-3.
Further, the acid catalyst is prepared by the following steps:
adding p-toluenesulfonic acid into deionized water at 80 ℃, then adding the modified carrier, stirring for 20-24h, evaporating the solvent after stirring is finished, and then drying for 2h at 120 ℃ to obtain an acid catalyst; the dosage ratio of the p-toluenesulfonic acid, the deionized water and the modified carrier is 5 g: 100mL of: 6-7 g.
Further, the modified support is prepared by the following steps:
step S11, mixing diatomite and a sodium hydroxide aqueous solution, stirring and mixing for 1h at the temperature of 25 ℃, then carrying out reduced pressure suction filtration, washing with deionized water and drying to obtain a solid a; the step is activating diatomite;
step S12, mixing the solid a with absolute ethyl alcohol, performing ultrasonic dispersion for 3min under the condition that the frequency is 40kHz to obtain a suspension, adding 3-aminopropyltriethoxysilane into the suspension, adjusting the pH value to 6 with acetic acid, stirring for 24h at the temperature of 40 ℃, performing suction filtration after stirring, washing with ethanol and deionized water, drying to constant weight at the temperature of 40 ℃ after washing to obtain a solid b, and introducing amino on the solid a through a silane coupling agent 3-aminopropyltriethoxysilane;
step S13, mixing epoxy chloropropane, ethylene glycol and boron trifluoride, stirring and reacting for 2 hours at 40 ℃, then adding tris (2-aminoethyl) amine and isopropanol, heating and refluxing for reaction for 4 hours, and after the reaction is finished, concentrating under reduced pressure to remove the solvent to obtain an intermediate 1;
the reaction process is as follows:
and step S14, mixing the intermediate 1, tetrahydrofuran and triethylamine, adding phosphorus oxychloride at the temperature of 20 ℃, stirring for reaction for 5 hours, then adding the solid b, keeping the temperature unchanged, and continuing stirring for reaction for 5 hours to obtain the modified carrier. Introducing amino on the surface of the diatomite to obtain a solid b; and (3) reacting the intermediate 1 with phosphorus oxychloride, and then reacting with the solid b to obtain the modified carrier containing the phosphate ester surfactant structure.
Further, the concentration of the aqueous sodium hydroxide solution in step S11 was 0.5mol/L, and the ratio of the amount of diatomaceous earth to the amount of the aqueous sodium hydroxide solution was 1 g: 25 mL;
the dosage ratio of the solid a, the 3-aminopropyltriethoxysilane and the absolute ethyl alcohol in the step S12 is 1 g: 0.6 g: 20 mL;
in step S13, the ratio of the amounts of epichlorohydrin, ethylene glycol, tris (2-aminoethyl) amine, isopropanol and boron trifluoride is 0.1 mol: 0.1 mol: 0.1 mol: 100mL of: 0.5 g;
in the step S14, the dosage ratio of the intermediate 1, phosphorus oxychloride, tetrahydrofuran, solid b and triethylamine is 2.5 g: 3 g: 50mL of: 5 g: 1g of the total weight of the composition.
The invention has the beneficial effects that:
the modified carrier is used as a raw material, p-toluenesulfonic acid is loaded to prepare the acid catalyst, so that the generation of chloride is avoided from the source, the alkali consumption is reduced, and the cleanness of the production process is expected to be realized. Meanwhile, the process flow is shortened, and the energy consumption is reduced.
The acidic catalyst contains the obtained phosphate ester surfactant structure, so that the reaction condition is milder, the generation of side reaction is reduced, the side reaction is inhibited, and the yield is improved under the condition that other processes for synthesizing glyphosate are the same. The phosphate group has excellent alkali resistance and good biodegradability, and the generated wastewater is easy to treat, thereby greatly reducing the cost. The acid catalyst obtained after loading is easier to recycle, and the continuity of the hydrolysis process is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a modified carrier:
step S11, mixing diatomite and a sodium hydroxide aqueous solution, stirring and mixing for 1h at the temperature of 25 ℃, then carrying out reduced pressure suction filtration, washing with deionized water and drying to obtain a solid a; wherein the concentration of the sodium hydroxide aqueous solution is 0.5mol/L, and the dosage ratio of the diatomite to the sodium hydroxide aqueous solution is 1 g: 25 mL;
step S12, mixing the solid a with absolute ethyl alcohol, performing ultrasonic dispersion for 3min under the condition that the frequency is 40kHz to obtain a suspension, adding 3-aminopropyltriethoxysilane into the suspension, adjusting the pH value to 6 with acetic acid, stirring for 24h at the temperature of 40 ℃, performing suction filtration after stirring, washing with ethanol and deionized water, and drying at the temperature of 40 ℃ to constant weight after washing to obtain a solid b; wherein the dosage ratio of the solid a, the 3-aminopropyl triethoxysilane to the absolute ethyl alcohol is 1 g: 0.6 g: 20 mL;
step S13, mixing epoxy chloropropane, ethylene glycol and boron trifluoride, stirring and reacting for 2 hours at 40 ℃, then adding tris (2-aminoethyl) amine and isopropanol, heating and refluxing for reaction for 4 hours, and after the reaction is finished, concentrating under reduced pressure to remove the solvent to obtain an intermediate 1; wherein the dosage ratio of the epichlorohydrin to the glycol to the tris (2-aminoethyl) amine to the isopropanol to the boron trifluoride is 0.1 mol: 0.1 mol: 0.1 mol: 100mL of: 0.5 g;
step S14, mixing the intermediate 1, tetrahydrofuran and triethylamine, adding phosphorus oxychloride at the temperature of 20 ℃, stirring for reaction for 5 hours, then adding the solid b, keeping the temperature unchanged, and continuing stirring for reaction for 5 hours to obtain a modified carrier; the dosage ratio of the intermediate 1, phosphorus oxychloride, tetrahydrofuran, solid b and triethylamine is 2.5 g: 3 g: 50mL of: 5 g: 1g of the total weight of the composition. Wherein the dosage ratio of the intermediate 1, phosphorus oxychloride, tetrahydrofuran, solid b and triethylamine is 2.5 g: 3 g: 50mL of: 5 g: 1g of the total weight of the composition.
Example 2
Preparing an acid catalyst:
adding p-toluenesulfonic acid into deionized water at 80 ℃, then adding the modified carrier, stirring for 20h, evaporating the solvent after stirring is finished, and then drying for 2h at 120 ℃ to obtain an acid catalyst; the dosage ratio of the p-toluenesulfonic acid, the deionized water and the modified carrier is 5 g: 100mL of: 6g of a mixture; the modified support was prepared as in example 1.
Example 3
Preparing an acid catalyst:
adding p-toluenesulfonic acid into deionized water at 80 ℃, then adding the modified carrier, stirring for 24 hours, evaporating the solvent after stirring is finished, and then drying for 2 hours at 120 ℃ to obtain an acid catalyst; the dosage ratio of the p-toluenesulfonic acid, the deionized water and the modified carrier is 5 g: 100mL of: 7g of a mixture; the modified support was prepared as in example 1.
Example 4
A method for continuously hydrolyzing glyphosate comprises the following steps:
step one, condensation: sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 35 ℃, and cooling to 30 ℃ after a reaction solution is clarified; adding glycine, heating to 50 ℃, and cooling to 35 ℃ after reaction liquid is clarified; adding dimethyl phosphite, heating to 45 ℃, cooling to 30 ℃ after the reaction liquid is clarified to obtain condensation liquid;
step two, hydrolysis: adding an acid catalyst into the obtained condensation liquid at the temperature of 20 ℃, heating to 40 ℃, reacting for 7 hours, and after the reaction is finished, filtering, crystallizing, suction filtering, washing and drying to obtain the glyphosate technical product. The yield of the product was 88.2%.
Wherein the dosage ratio of methanol, paraformaldehyde, triethylamine, glycine and dimethyl phosphite is 20 mL: 1.5 g: 2.5 g: 2 g: 3.5 g; the dosage ratio of the acidic catalyst to the glycine is 1: 2. the acid catalyst was prepared as in example 3.
Example 5
A method for continuously hydrolyzing glyphosate comprises the following steps:
step one, condensation: sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 40 ℃, and cooling to 35 ℃ after a reaction solution is clarified; adding glycine, heating to 55 ℃, and cooling to 35 ℃ after reaction liquid is clarified; adding dimethyl phosphite, heating to 50 ℃, cooling to 35 ℃ after the reaction liquid is clarified to obtain condensation liquid;
step two, hydrolysis: adding an acid catalyst into the obtained condensation liquid at the temperature of 20 ℃, heating to 45 ℃, reacting for 7 hours, and after the reaction is finished, filtering, crystallizing, suction filtering, washing and drying to obtain the glyphosate technical product. The yield of the product was 88.5%.
Wherein the dosage ratio of methanol, paraformaldehyde, triethylamine, glycine and dimethyl phosphite is 20 mL: 1.5 g: 2.5 g: 3 g: 3.5 g; the dosage ratio of the acidic catalyst to the glycine is 1: 2. the acid catalyst was prepared as in example 3.
Example 6
A method for continuously hydrolyzing glyphosate comprises the following steps:
step one, condensation: sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 50 ℃, and cooling to 40 ℃ after a reaction solution is clarified; adding glycine, heating to 60 ℃, and cooling to 40 ℃ after reaction liquid is clarified; adding dimethyl phosphite, heating to 55 ℃, cooling to 45 ℃ after the reaction liquid is clarified to obtain condensation liquid;
step two, hydrolysis: adding an acid catalyst into the obtained condensation liquid at the temperature of 25 ℃, heating to 50 ℃, reacting for 7 hours, and after the reaction is finished, filtering, crystallizing, suction filtering, washing and drying to obtain the glyphosate technical product. The yield of the product was 88.1%.
Wherein the dosage ratio of methanol, paraformaldehyde, triethylamine, glycine and dimethyl phosphite is 20 mL: 1.5 g: 2.5 g: 3 g: 3.5 g; the dosage ratio of the acidic catalyst to the glycine is 1: 3. the acid catalyst was prepared as in example 3.
Comparative example 1
Adding p-toluenesulfonic acid into deionized water at 80 ℃, then adding diatomite, stirring for 24 hours, evaporating the solvent after stirring is finished, and then drying for 2 hours at 120 ℃ to obtain an acid catalyst; the dosage ratio of the p-toluenesulfonic acid, the deionized water and the diatomite is 5 g: 100mL of: 7 g.
Comparative example 2
The acidic catalyst of example 5 was converted to the sample prepared in comparative example 1, and the remaining raw materials and preparation process were kept unchanged. The yield of the product was 72.5%.
From the product yields of examples 4-6 and comparative example 2, it can be seen that the yield is improved when the acid catalyst prepared according to the present invention is added, under the same conditions as other processes for synthesizing glyphosate.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A method for continuously hydrolyzing glyphosate is characterized by comprising the following steps:
firstly, sequentially adding methanol, paraformaldehyde and triethylamine into a condensation kettle, heating to 35-50 ℃, and cooling to 30-40 ℃ after reaction liquid is clarified; adding glycine, heating to 50-60 deg.C, and cooling to 35-40 deg.C after reaction solution is clarified; adding dimethyl phosphite, heating to 45-55 ℃, cooling to 30-45 ℃ after the reaction liquid is clarified to obtain condensation liquid;
and secondly, adding an acid catalyst into the obtained condensation liquid at the temperature of 20-25 ℃, reacting at the temperature of 40-50 ℃, and filtering, crystallizing, suction filtering, washing and drying after the reaction is finished to obtain the glyphosate technical product.
2. The method for continuously hydrolyzing glyphosate according to claim 1, wherein the acidic catalyst is prepared by the following steps:
adding p-toluenesulfonic acid into deionized water at 80 ℃, then adding the modified carrier, stirring for 20-24h, and carrying out post-treatment to obtain the acid catalyst.
3. The process of claim 1, wherein the reaction time in the second step is 7 hours.
4. The method for continuously hydrolyzing glyphosate according to claim 2, wherein the post-treatment process in the preparation process of the acid catalyst is as follows: after stirring, the solvent was evaporated to dryness and dried at 120 ℃ for 2 h.
5. The method of claim 1, wherein the ratio of methanol to paraformaldehyde to triethylamine to glycine to dimethyl phosphite is 20 mL: 1.5 g: 2.5 g: 2-3 g: 3.5 g; the mass ratio of the acid catalyst to the glycine is 1: 2-3.
6. The method for continuously hydrolyzing glyphosate according to claim 2, wherein the modified carrier is prepared by the following steps:
step S11, mixing diatomite and a sodium hydroxide aqueous solution, stirring and mixing for 1h at the temperature of 25 ℃, then carrying out reduced pressure suction filtration, washing with deionized water and drying to obtain a solid a;
step S12, mixing the solid a with absolute ethyl alcohol, performing ultrasonic dispersion for 3min under the condition that the frequency is 40kHz to obtain a suspension, adding 3-aminopropyltriethoxysilane into the suspension, adjusting the pH value to 6 with acetic acid, stirring for 24h at the temperature of 40 ℃, performing suction filtration after stirring, washing with ethanol and deionized water, and drying at the temperature of 40 ℃ to constant weight after washing to obtain a solid b;
step S13, mixing epoxy chloropropane, ethylene glycol and boron trifluoride, stirring and reacting for 2 hours at 40 ℃, then adding tris (2-aminoethyl) amine and isopropanol, and heating and refluxing for reacting for 4 hours to obtain an intermediate 1;
and step S14, mixing the intermediate 1, tetrahydrofuran and triethylamine, adding phosphorus oxychloride at the temperature of 20 ℃, stirring for reaction for 5 hours, then adding the solid b, keeping the temperature unchanged, and continuing stirring for reaction for 5 hours to obtain the modified carrier.
7. The method of claim 6, wherein the concentration of the aqueous solution of sodium hydroxide in step S11 is 0.5mol/L, and the ratio of the diatomite to the aqueous solution of sodium hydroxide is 1 g: 25 mL;
the dosage ratio of the solid a, the 3-aminopropyltriethoxysilane and the absolute ethyl alcohol in the step S12 is 1 g: 0.6 g: 20 mL;
in step S13, the ratio of the amounts of epichlorohydrin, ethylene glycol, tris (2-aminoethyl) amine, isopropanol and boron trifluoride is 0.1 mol: 0.1 mol: 0.1 mol: 100mL of: 0.5 g;
in the step S14, the dosage ratio of the intermediate 1, phosphorus oxychloride, tetrahydrofuran, solid b and triethylamine is 2.5 g: 3 g: 50mL of: 5 g: 1g of the total weight of the composition.
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